JP4855247B2 - Water-wax emulsion and its coating application - Google Patents

Description

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION Emulsions prepared using plant-derived waxes are used in many applications, such as being applied to fiber cellulose products such as paper and wood for the purpose of making them moisture resistant. It can also be used for products. These emulsions are used as fruit coatings for the purpose of improving moisture resistance. The emulsion contains water, vegetable wax and surfactant. Plant waxes from sources such as castor oil, palm or soybean contain triglycerides having a melting point in the range of about 136-200 ° F. The solid content of the emulsion may be as high as 45% with respect to the total weight of the emulsion.

2. 2. Description of Related Art Wax-based emulsions are applied to a large number of industrial cellulose products such as paper, corrugated paper, kraft paper, cardboard and other fibrous cellulosic products, for example, for the purpose of imparting moisture resistance to the product. It is used for various purposes. Wax emulsions typically contain about 15% to 40% (by weight) wax with about 5% to 25% surfactant added to the weight of the wax. Emulsions are used in place of molten wax applications because they are easy to handle, apply and blend with other aqueous base ingredients. Once prepared, the emulsion can remain stable over a long period of time (ie, without separation into its components). This stability facilitates factors such as transportation from the manufacturer to the end user, storage, and use in specific applications. On the other hand, in order to apply the molten wax, the wax needs to be maintained in a molten state and melted as necessary, and needs to be applied in a molten state.

  Wax emulsions are generally produced in a batch reactor or using a homogenizer. It is important that the equipment used to prepare the emulsion can stir the reactants to achieve thorough mixing and have proper temperature control to maintain sufficient heating and cooling of the reactants and products. In general, it is known that the use of a homogenizer increases the percentage of solids in the final emulsion product as compared to emulsions prepared using mixing in conventional stirred batch reactors. Both types of equipment are often used to produce the emulsions of these inventions.

  For certain applications, it is preferred to use an emulsion having a wax solids content as high as is practical. For example, when treating products such as paper products, fruits or medicines with waxes, it is preferable to minimize the drying time of the treated products, and one means to achieve this goal is to have a high wax solids content. It is to use the emulsion which has. If the emulsion has to be transported over long distances, reducing the volume helps to reduce transport costs. Aqueous emulsions are also preferred over organic solvent based emulsions (or dispersions) due to environmental pollution or adverse health and safety concerns.

  Wax-based emulsions are generally formulated to have a specific ionic charge, with the goal of being compatible with other ingredients that are usually later formulated with the wax emulsion. The wax emulsion may be either anionic, nonionic or cationic depending on the emulsifier used to make the wax emulsion (generally a surfactant such as a surfactant). .

  The wax to be emulsified must have some functional groups such as carboxyl, acid or ester groups attached to the wax polymer. In the emulsification process, these functional groups are saponified to become more hydrophilic, thus allowing the desired surfactant to form micelles around the wax. Commonly used bases for saponifying wax functional groups include potassium hydroxide (KOH), sodium hydroxide (NaOH), and ammonia, diethylamino ("DEA") and other amine derivatives. Examples include amines. To prepare specific emulsion types, acids such as glacial acetic acid or similar acids are used for functional group modification. The amount of functional group that needs to be modified to form a stable emulsion can vary depending on the properties of the wax, such as molecular weight and the amount of chain branching. In general, waxes with about 20-30 mg KOH / g wax and the lowest saponification number can be easily emulsified. The saponification number or saponification number is the milligram amount of KOH that reacts with 1 g of wax at high temperature and indicates the total amount of free carboxylic acid and any ester that can be saponified. This value, and the acid value described below, provide an indication of the free carboxylic acid and ester content of the wax. An example of how to determine the saponification number is ASTM D1387. ASTM D1386 is a method of determining the acid number; the amount of milligrams of KOH required to neutralize 1 g of wax, indicating the amount of free carboxylic acid present.

  The general first step in the emulsification process is to add enough base to dissolve the wax (if necessary) and saponify the desired number of functional groups on the wax. The surfactant is then added and stirred well to form an emulsion. When a homogenizer is used for producing an emulsion, the particle size of the resulting wax emulsion is affected by the shearing action of the homogenizer. When preparing emulsions using a homogenizer, saponification of the wax is less important due to the mechanical shearing contribution of the wax. In general, the most stable emulsions (generally having the smallest particle size) are made using a combination of saponification and good mixing.

  Parameters that typically characterize the quality of the emulsion once formed include the clarity and stability of the emulsion. Stability is generally measured as the degree of separation into components of the emulsion after a long period of time.

  The hardness defined by ASTM D1321 and ASTM D-5 relates to the distance (1 / 10th of a millimeter, dmm) a special needle passes through the wax under a given temperature and a given weight. “Soft” waxes have hardness properties that pass over 10 mm and are considered less useful, but waxes with hardness values that pass less than 10 mm are considered more useful in these preparations. The color of a particular wax formulation varies from batch to batch even with the same wax. The overall color of the solidified wax formulation is affected by factors such as the cooling rate of the wax, the amount of occluded air, and the surface treatment. In general, the color of the wax for a molten wax formulation is determined using either the ASTM D1500 (Gardner) or ASTM D156 (Siebold) method. The ASTM D1500 method is typically used to measure dark brown to off-white colors, while the ASTM D156 method is used to measure off-white to pure white.

For applications such as food or pharmaceutical tablet coatings, it is preferred to use waxes characterized by having low pass hardness and good color properties (toward the white end against the brown end of the color scale)
Wax emulsions are often used by themselves or in combination with other ingredients when coated on paper, paperboard, cardboard, or other paper products to impart moisture resistance thereto. For example, foods such as fish or vegetables such as broccoli are frequently packaged and transported in wax-coated paper boxes. The wax coating helps maintain the strength and quality of the packaging in the presence of ice in the packaging, in humid environments such as transport in refrigerated vehicles and refrigerated environments. Depending on the end use application, other properties such as gloss, slip resistance and printability of the final paper product or on the final paper product are also affected by the wax coating. Wax coated packaging is usually discarded once used.

  There is a growing domestic and international trend to recycle paper products once packaged products have been used and the wax coated packaging has been disposed of by the consumer. However, in the recycling process, the wax coating on the packaging tends to form what is known in the industry as "stickies" and "stickies", which causes problems to the recycling equipment due to its presence. is there. This problem is so common that in some places it is necessary to exclude wax-coated paper products from the recycling process. As a result, the wax-coated articles are separated and incinerated or disposed of in landfills instead of being recycled. Use of additives added to the wax (US Pat. No. 6,255,375 to Mitchellman and US Pat. No. 6,273,993; US Pat. No. 6,416,620 to Naransic et al .; and Alternative techniques have been proposed and used to minimize wax incorporation into the recycling process, such as US Pat. No. 6,053,439). Neither of these approaches is permanently accepted as a solution to the problems associated with waxes in the recycling process.

  Commercial sources of oil-derived waxes include CITGO, ExxonMobil, Shell Oil and the like. Most of these waxes originate from a lubricating oil purification process, in which the wax is separated from the lubricating oil fraction and purified into various wax fractions including paraffin and microcrystalline wax. Additional commercial sources of waxes include manufacturers such as Astor Wax, IGI, and Moore & Munger that supply waxes for prior art applications. These waxes are often resold “as is” from oil companies and / or formulated and repackaged to meet specific consumer requirements. Other commercial suppliers, often referred to as “emulsion houses”, such as Michelman (Ohio) and ChemCore (New York), use various waxes for coatings and other applications. Convert to

  The prior art describes the use of petroleum-derived waxes and synthetic waxes for incorporation into emulsions, but does not mention the use of plant-derived waxes in emulsions. Considering that the world's oil supply is finite and depleted, there is a long-term need to develop alternatives to petroleum-derived products such as petroleum waxes from limited natural resources that are declining in supply. Recognized. Since wax emulsions are frequently used in food packaging applications, waxes with food grade properties are also preferred for safety. The need to use in emulsions materials that are naturally derived and can be easily recycled to the environment without long-term adverse effects has also been recognized for a long time; for example, having wax-based coatings and adhesives Corrugated boxes are known to be difficult to recycle. Accordingly, it is also required to employ waxes having properties similar to those of petroleum-derived or synthetic waxes used in emulsion formulations. Also readily available compositions are preferred because large amounts of wax are consumed for these applications. From both supply and natural resource perspectives, the composition is preferably obtained from a renewable source, such as from a plant extract. Therefore, it is preferable that the wax does not need to be imported and can be produced at a cost that can compete with petroleum-derived wax such as paraffin and microcrystalline wax.

  There is a need for waxes that can be converted to anionic, cationic or nonionic emulsions, have relatively high melting points, low viscosity, excellent moisture barrier properties, and thermally stable waxes. . Also, considering the global oil supply described above, the wax is preferably one that can be obtained from a renewable source, such as a plant, rather than one derived from petroleum. The wax used in the present invention satisfies these requirements.

  The present invention relates to emulsions prepared with vegetable oils containing triglycerides and having a melting point of about 136-200 ° F. (50-95 ° C.). These wax emulsions are used in various applications such as paper and wood coatings, brightener and cosmetic applications, inks, paints and adhesives; and gypsum products to improve fruit coating and moisture resistance.

  The present invention relates to a series of waxes obtained by curing one or more vegetable oils. When highly cured, the oil properties are modified to become wax-like with a high melting point, low viscosity and excellent hardness. The wax of the present invention is also unique in that it has a high degree of functional groups. By modifying a part of the functional group on the wax of the present invention, the wax of the present invention can be easily emulsified. More unexpectedly, it has been found that the waxes of the present invention can also be easily recycled because it can further saponify the functional groups on the wax, thereby making the wax more hydrophilic. Yet another unexpected finding is that the saponified wax is free of ink and adhesive litter during the recycling process because the density of the wax is relatively low and the wax can float and carry the ink, adhesive and litter. It can promote separation.

  Wax emulsions mainly consist of water, surfactants (which are cationic, nonionic or anionic, depending on the desired properties for a particular emulsion), and acids or bases (often KOH, NaOH or various amines). Selected from one of these). Other ingredients such as biocides or stabilizers can be added, as is well known to those skilled in the art. Although biocides and / or antimicrobial agents can be added to the emulsion, the selection of a specific biocide or antimicrobial agent often depends on the end use of the emulsion. Biocides that can be used include parabens such as methyl or ethylhydroxyparabenzoic acid, or quaternary ammonium compounds, other compounds well known to those skilled in the art. The waxes used in the formulations of the present invention are of natural origin, are readily available, are generally considered safe and have a relatively high melting point with excellent altitude and color, so It can be used in place of undesired synthetic waxes (often derived from petroleum such as polyethylene) or in place of less readily available naturally occurring waxes such as montan or carnauba alone.

  Furthermore, the wax used in the present invention can be easily removed from applied articles such as cardboard and paper. Since these waxes can be easily modified, such removal is carried out under conditions considered to be common for paper recycling (dispersed in a warm alkaline aqueous mixture and stirred). Furthermore, due to the relatively low density of the waxes used in the present invention, the inventors suspended the wax from the paper during the paper recycling process, along with ink and other recycled waste with itself for easy skimming and removal. It has been found that separation of ink and other garbage in the paper recycling process is facilitated. Since removal of these waxes from the treated product is easy, emulsions containing such waxes may require the lubricating and sizing properties of the wax in spinning and / or weaving processes, etc. Or it is suitable for use in fiber applications where it is preferred that the wax be removed at a later stage such as desizing. The biodegradability of the new wax makes it particularly suitable for disposal in a landfill that can handle natural organic materials. The use of novel wax emulsions on fruits has also been shown to have useful properties through the ability to reduce moisture transpiration and extend the shelf life of produce.

  The present invention discloses natural waxes used to make emulsions. The wax is a commercially available high triglyceride wax obtained by processing commodities containing natural oils such as soybean, palm, castor, canola and other grains from which oil is obtained. Vegetable oils with different degrees of hardening are used in the food industry. As cooking oil, unsaturated oil is preferable. Commercially available but highly cured waxes used in the present invention have not been so widely produced or used due to limited applications in the food industry. The wax used in the present invention is commercially available. The materials are Archer Daniels Midland (Dicator III), indicated by its product number 86-197-0, Cargill Incorporated (Wyata, Minnesota), indicated by its product number 800mrcs0000u, and others under the generic name "Hardened Soybean Oil" Processed and supplied by the source. Palm oil wax was supplied by Custom Shortenings and Oils (Richmond, VA) and designated as its product number Master Chef Stable Flakes-P. A mixture of hydrogenated castor oil and soybean wax is also sold under the trademark STEFOTEX and is obtained from the abitec group (columbus, OH, a blend and blender of vegetable oil-derived waxes). It was.

SUMMARY OF THE INVENTION An object of the present invention is to provide a wax composition that can be formulated into an aqueous wax emulsion.

  Another object of the present invention is to provide a series of stable emulsions prepared with plant derived waxes.

  Another object of the present invention is to later apply to articles such as paper, paperboard, cardboard, other cellulosic products, etc. to make them moisture resistant for use in consumer packaging and other industrial applications. It is to provide a wax-based emulsion that can be applied.

  Yet another object of the present invention is to provide a composition that can be incorporated into wax-based emulsion formulations as an alternative to petroleum-derived waxes currently used in many wax-based emulsion formulations.

  Another object of the present invention is to provide a composition that, when formulated in a wax-based emulsion formulation, is compatible with the other ingredients of the formulation and forms a stable emulsion.

  Yet another object of the present invention is that when the coating formulation is applied to an article for the purpose of imparting moisture resistance, it is incorporated into an emulsion used to coat paper or other cellulosic goods. It is to provide a composition having properties similar to the coating properties of conventional wax-based emulsion formulations prepared with the derived wax.

  Yet another object of the present invention is to provide a composition that can be obtained from renewable resources instead of a non-renewable petroleum-based composition.

  Yet another object of the present invention is more economical to use for applications involving cellulosic products and coatings of other products, and thus to a wax that is naturally derived but more expensive and less accessible (eg, carnauba). It is to provide a naturally occurring composition that can be substituted.

  Yet another object of the present invention is more economical to use in applications involving fruit coatings to reduce moisture transpiration and extend the shelf life of agricultural products, and thus are naturally derived but more expensive. It is to provide a naturally-derived composition that can replace a hard-to-obtain wax (eg, carnauba).

  Yet another object of the present invention is to provide a composition that can be obtained from renewable resources and can be produced economically.

  Another object of the present invention is to provide a composition having properties that are normally considered safe by the Food and Drug Administration (FDA) for use in food packaging and coating.

  The inventors have unexpectedly found that highly hardened oils such as palm and soy can be effectively used as an alternative to conventional petroleum and synthetic waxes in wax-based emulsion compounds. And found that it can be converted.

The present invention produces an emulsion that has wax-like properties and is blended into a water emulsion using conventional emulsification methods to have similar barrier and coating properties to emulsion formulations containing petroleum-derived waxes. Contains highly hardened vegetable oils (obtained from palm, soybean, corn, castor, canola, etc.). According to the waxes of the present invention obtained from naturally derived renewable resources, emulsions have been produced which are emulsified under anionic, cationic and nonionic conditions and have a solids content of up to about 45% solids. . Soy wax and coconut wax substantially contain more than 90% triglycerides, and their fatty acid components are from hardened oils containing palmitic acid and stearic acid (stearic acid (C ₁₈ ) is more predominant (greater than 50%)). Become. In contrast, castor oil contains about 1% stearic acid and ricinoleic acid (about 90%) as the main component. The wax composition has a low iodine number (between 2-5) and a melting point (Mettler Drop Point) between about 120-185 ° F. The wax composition of the present invention may also be used as an additive in the manufacture of fibrous cellulosic products such as wax-coated boxes (coating) that can be more easily recycled later than boxes prepared using conventional waxes. As). When used to coat fibrous cellulosic products such as paperboard, the performance of the emulsion was similar to an emulsion containing petroleum derived wax. The wax emulsions of the present invention can also be used by themselves or in combination with other ingredients as a coating to reduce the transpiration of foods such as fruits or other agricultural products or to extend the shelf life. Can be. The waxes of the present invention are used as an alternative to petroleum derived waxes or more expensive naturally derived waxes in coatings, brighteners, adhesives, paper products, paperboard and other manufacturing operations.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a process for producing a hardened oil.

  FIG. 2 shows the effect of citrus fruit coating with soy wax based emulsion on weight loss.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The present invention relates to emulsions prepared using plant-derived wax compositions that can be used as a substitute for petroleum-derived waxes. More particularly, the present invention discloses a wax emulsion in water prepared using a plant-derived wax composition. Because the waxes used in the present invention can be economically produced from renewable sources, the waxes are also naturally derived but more expensive to produce in various applications described herein. The properties of coatings containing petroleum-derived or synthetic waxes, or naturally-occurring waxes such as carnauba, may be substituted (see Table 3). Naturally derived waxes and synthetic waxes include, but are not limited to, cosmetics, foods, lubricants, personal hygiene, pharmaceuticals and brighteners for consumer and industrial applications, such as floor brighteners, etc. Widely used in a wide range of industry representatives. Other applications include fabric softeners and sizing agents, fruit coatings, water-based inks and paints, gypsum, coatings for building materials such as particleboard, paper products such as corrugated paper, paperboard, cardboard base paper, laminated paper, As well as a fertilizer coating. The term wax is used to denote a wide variety of organic esters and wax-like compounds, the chemical structure is diverse and exhibits a wide range of melting points. Depending on the ambient temperature, the same compound can often be referred to as “wax”, “fat” or “oil”. Whatever name the compound is named, the choice of wax for a particular application is determined by whether the wax is liquid or solid at the temperature of the product in which the wax is used. There is often. Often the wax needs to be highly purified and chemically modified in order to be useful for a given purpose. Despite such efforts for modification, many physical properties of the wax still prevent the wax from being used favorably, or are highly and frequently used to make the wax commercially available. However, expensive and further processing is required.

  Triglycerides are fatty acid esters of glycerol. As used herein, the term “free fatty acid” shall mean a fatty acid that is not covalently bonded to glycerol via an ester bond. The term “fatty acid component” is used to describe a fatty acid that is covalently bonded to glycerol via an ester bond.

  Naturally occurring carboxylic acids ("fatty acids") and derivatives thereof, more commonly glyceryl derivatives in which all three hydroxy groups of the glycerol molecule are esterified with carboxylic acids are used commercially. The carboxylic acid may be saturated or unsaturated. Tri-substituted glycerol (also called triglyceride, triacylglycerol) is the main component of most animal and vegetable fats, oils and waxes. When all three hydroxy groups of a glycerol molecule are esterified with the same fatty acid, the trisubstituted glycerol is referred to as a monoacid triglyceride. Whether triglycerides are referred to as “wax”, “fat” or “oil”, in addition to the ambient temperature at which the characterization is made, the chain length of the esterified acid and its saturated or unsaturated Depends on the degree. In general, as the degree of saturation of the esterified acid increases and the chain length increases, the melting point of the triglyceride increases. Many commercially used triglycerides and free fatty acids are preferably obtained from plant sources such as soybean, canola, cottonseed, corn, orange, flaxseed, palm, peanut, safflower, soybean, and sunflower oil . Triglycerides are used after being purified using methods well known to those skilled in the art such as, but not limited to, solvent extraction of plant biomass with aliphatic solvents to obtain plant triglycerides. Subsequent additional purification includes distillation, fractional crystallization, degumming, bleaching, and steam distillation. The resulting triglycerides are partially or completely cured. In addition, fatty acids can be obtained by hydrolysis of natural triglycerides (eg, alkaline hydrolysis followed by purification by methods well known in the art such as distillation and steam distillation) or by synthesis from petrochemical fatty alcohols. Also good. Free fatty acids, triglycerides and the like may also be obtained from commercial sources such as Cargill, Archer Daniels Midland and Central Soya.

In the present invention, the fatty acid components of free fatty acids and triglycerides are saturated and have various chain lengths. If the coating composition is solid at the temperature at which the coating is used, the free fatty acid and fatty acid component of the triglyceride may be unsaturated. Properties such as the melting point of the free fatty acid / triglyceride mixture vary as a function of the chain length and saturation of the free fatty acid and the fatty acid component of the triglyceride. For example, as the degree of saturation decreases, the melting point decreases. Similarly, as the chain length of the fatty acid decreases, the melting point decreases. Preferred free fatty acids are saturated fatty acids such as palmitic acid, oleic acid, stearic acid, arachidonic acid and behenylic acid. Stearic acid ( _C18 saturated fatty acid) is more preferred. Ricinoleic acid ((9Z, 12R) -12-hydroxy-9-octadecenoic acid) is a _C18 hydroxy unsaturated fatty acid. As described further below, ricinoleic acid is the main component of castor oil and castor wax, containing low concentrations of oleic acid, linoleic acid and palmitic acid.

  The iodine value “IV”, also referred to as iodine number, is a measure of the degree of saturation or unsaturation of a compound. As the iodine value, the amount of iodine absorbed by the compound or mixture in a predetermined time is measured. Thus, when used with unsaturated materials such as vegetable oils, IV is a measure of the number of unsaturated or double bonds in the compound or mixture.

  Vegetable oils or animal fats can be synthetically cured using methods well known to those skilled in the art to have a low or very low iodine number. Fats consisting primarily of saturated triglycerides (eg coconut oil or fractionated fat) are used alone or in mixed formulations with adhesives / laminates to improve water resistance as a composite material. (U.S. Pat. No. 6,277,310). The main component of vegetable oil is triacylglycerol.

  Saturated triglycerides having low iodine numbers (ranging from about 0 to about 70 iodine numbers, preferably ranging from about 0 to about 30 iodine numbers) are soybeans, soybean stearin, stearin, corn, cottonseed, rapeseed, canola, It can be made by curing commercially available oils such as sunflower, palm, palm kernel, coconut, cranberry, flaxseed, peanut oil, fish oil and tall oil; or animal fats such as lard and tallow, and mixtures thereof. These oils may also be produced from genetically modified plants to obtain low IV oils with a high proportion of fatty acids.

  Fat is generally fractionated by a process known as “winterization” that cools the mixture for a time long enough for a harder fraction of the fat to crystallize. After this cooling, filtration is performed so that a harder fraction is retained in the filter cake. These harder fractions have a lower iodine number and thus have a higher melting point than that of the separated original fat. Thus, dewaxing can also be used as a source of low IV fat.

  The above dewaxing process is generally used to fractionate animal fats, and thus can produce various animal fat fractions with different iodine numbers and consequently different chemical properties. is there. These fractions may be mixed with fatty acids and free fatty acids obtained from other sources such as the plants or plant extracts described above.

  Wax-based emulsions are commonly used in the manufacture of corrugated paper, cardboard boxes and the like. They are also used in a variety of applications, such as floor brighteners, fiber softeners and sizing agents, fruit coatings, cosmetic formulations, aqueous inks and paints, gypsum manufacture, and fertilizer coatings. In many of these applications, the properties of the wax that prevent moisture transpiration are important for performance. The waxes of the present invention have been shown to have moisture transpiration prevention properties comparable to paraffin wax (see Table 5).

  Emulsions are used at various concentrations and addition levels depending on the application. For example, in fruit coating applications, the wax may comprise the majority of formulations that often also contain shellac to impart a gloss to the fruit. In paper applications, or when used in other fibrous cellulosic products, the wax-based emulsion can be used as is (ie, undiluted) or when formulated in a coating or sizing formulation. It may be diluted. Such applications are usually associated with favorable ionic charges. For example, for fibers, cationic wax emulsions have a better affinity for fibers or fabrics than anionic or nonionic emulsions, and cationic emulsions generally help the wax collect fibers / fabrics. Used. Surfactants (ie, surfactants), also called emulsifiers, include nonylphenol ethoxylates and ethoxylates available from other commercial sources. For example, alcohol ethoxylate, alkylamine ethoxylate, alkylphenol ethoxylate, octylphenol ethoxylate and the like can be mentioned. Other surfactants such as many fatty acid esters; for example, but not limited to, glycerol esters, polyethylene glycol esters and sorbitan esters, and amidated fatty acid esters such as tallow amine may be used.

  Nonionic surfactants that can be used include Igepal (registered trademark) trademarks such as IGEPAL (registered trademark) CO-630 (CAS number 68412-54-4) (Rhodia, Inc., Cranberry, New Jersey). State) or POLYSTEP® F-3 (Stepan Co., Northfield, Ill.) Nonylphenyl ethoxylates; alkylphenol ethoxylates; Octylphenol ethoxylates such as CA series compounds; decylphenol ethoxylates; oleyl alcohol ethoxylates; NONIDET NP-40 (CAS No. 9016-45-9) Etc. Other non-ionic surfactants that may be used include the HLB 10.5 Tomadol® 25-3 / 25-9 combination (Tomah Chemical Corp., Milton, Wis.) , A mixture of ethoxylated linear alcohol non-ionic surfactants) or a combination of HLB 10.5 TERGITL® 15-S-5 / 15-S-9 (Dow Chemical, Midland) Michigan).

  In general, the surfactants used have a specific range of HLB values, and surfactants having similar properties may be used instead.

  Cationic surfactants include imidazolines such as imidazoline, diethylamine, or tallow amines such as TAM-5 or TAM-15. The above-mentioned surfactant used has a specific range of HLB values, and a surfactant having similar characteristics may be used instead.

  Specific surfactants used to remove ink from paper include those from the ANTAROX (Rodia Inc., Cranberry, NJ) group. These compounds include nonionic dispersants, ethylene oxide-propylene oxide copolymers, nonylphenol ethylene oxide-propylene oxide, and poloxamers. Companies such as ONDEO Nalco of Naperville, Illinois also supply custom mixed surfactants that are prepared to meet specific consumer deinking and repulping requirements.

  The present invention relates to emulsions prepared using vegetable waxes containing triglycerides and having a melting point of about 136-200 ° F. The present invention uses hardened triglycerides, which have a iodine value close to zero and make the triglycerides more thermally stable. The triglyceride can be selected from those having an iodine value between 0 and 30, but triglycerides having an iodine value between 2 and 5 are preferred.

  As mentioned above, wax emulsions are mainly composed of water, surfactants (which are either cationic, nonionic or anionic, depending on the properties desired for a particular emulsion) and acids or bases (often KOH , NaOH, or various amines).

  Other ingredients such as biocides or other stabilizers may be added to the emulsion and these agents are well known to those skilled in the art. Biocides and / or antimicrobial agents may be added to the emulsion, and the selection of a particular biocide or microbicide often depends on the end use of the emulsion. Biocides that can be used include parabens such as methyl or ethylhydroxyparabenzoic acid, or quaternary ammonium compounds, other compounds well known to those skilled in the art. Buffers and thickeners well known to those skilled in the art may be added to the emulsions of the present invention. Common preservatives such as formaldehyde are sometimes used and are subject to regulation by regulatory agencies such as the Food and Drug Administration (FDA) and the Environmental Protection Agency (EPA).

  The waxes used in the preparation of the present invention are naturally derived, readily available, generally considered safe, and have a relatively high melting point with excellent hardness and color, so these waxes are less preferred synthetic waxes It can be used instead of (often derived from petroleum such as polyethylene) or in place of a less readily available natural wax such as montan or carnauba alone.

  The present invention is a natural wax for use in wax-based emulsion formulations. This product is a commercially available high triglyceride wax obtained by processing commodities containing natural oils such as soybeans, palm, castor, canola and other grains from which oil is obtained. The wax used in the present invention is a combination of coconut oil wax and soybean wax, and castor oil prepared from hydrogenated oil. Materials are: Cas Chem (Baion, NJ), Archer Daniels Midland (Dicator III), shown with its product number 86-197-0; Cargill Inc. (Wyata, MN), shown with its product number 800 mrcs0000u ); And other sources under the generic name “hardened soybean oil”. Palm oil wax was supplied by Custom Shortenings and Oils (Richmond, VA) and was designated as its product number Master Chef Stable Flakes-P. Soy wax was also supplied by Marcus Oil and Chemical Corp., Houston, TX, under the trade name Marcus Nat 155; these additives are also food additives Can also be used.

  The properties of soy wax and palm wax are summarized in Tables 1 and 2, which are shown to have an IV between 5 and 2, respectively.

  When measured as a Mettler dropping point, soybean oil wax has a melting point of 155-160 ° F, whereas palm oil wax has a melting point of 136-142 ° F.

  Palm wax and soy wax are further characterized by having a viscosity of 10-200 cps at a temperature of 210 ° F. Palm wax and soy wax each contain 93% by weight triglycerides along with trace amounts of fatty acids. The triglyceride can be saponified by the addition of a base such as KOH to obtain a saponification value. The saponification number varies mainly depending on the chain length of the fatty acid, which is a function of the source of vegetable wax. The saponification value for hardened soybean wax and hardened palm wax is usually in the range of 180-200 mg KOH / g (Tables 1 and 2).

Analysis of the fatty acid content of coconut wax and soy wax using well known methods of gas liquid chromatography (“GLC”) reveals that soy wax is 82-94% stearic acid (C _{18: 0} ) and 3-14% palmitic acid. It was found to contain (C _{16: 0} ). In comparison, coconut oil wax is about 55% stearic acid (C _{18: 0} ), 39.5% palmitic acid (C _{16: 0} ), 1.1% myristic acid (C _{14: 0} ) and Contains about 1.0% oleic acid ( _{C18: 1} ).

Castor wax is obtained from castor oil in the same way that soy wax and palm wax are prepared from their corresponding oils. Castor oil is a natural oil obtained from the seeds of castor plant. Castor oil is about 90% ricinoleic acid ((9Z, 12R) -12-hydroxy-, a C ₁₈ hydroxy unsaturated fatty acid having a double bond at the 9-10 position and a hydroxyl group on the 12th carbon). It is unique among all fats and oils in that it is the only commercially important oil containing 9-octadecenoic acid). The fatty acid composition of castor oil is described as 37% ricinoleic acid, 3% linoleic acid, 2% palmitic acid, 1% stearic acid and trace amounts of dihydrostearic acid (Merck Index, 13th edition) , 2001, Merck & Company, Inc., White House Station, NJ). The main sources of castor oil are India, China and Brazil. Scientific and historical records indicate that the chemical nature and composition of castor oil is very uniform, regardless of its origin.

  Castor wax, also called hydrogenated castor oil, is a catalytically hardened castor oil (hardening of castor oil in the presence of a nickel catalyst). Castor wax is a hard, brittle wax well known to those skilled in the art that is almost insoluble in water and usually used in organic solvents. The wax has a melting point of about 84-88 ° C. (about 183-185 ° F.), an acid number of 2-3 (mg KOH / g), a saponification number of about 174-186 (mg KOH / g), and 3 Characterized by having an iodine number of ~ 4 (Table 3).

  Castor wax has been used to prepare coatings that are water repellent or resistant to oils, petroleum and petroleum derivatives. Castor wax is mainly used in the production of grease, but castor oil is also used in paper coatings for food packaging and cosmetic applications, and castor wax derivatives are used as surfactants and plastic additives. . Note the difference in stearic acid content in these waxes, palm wax and soy wax have 84-92% stearic acid, whereas only about 1% stearic acid is present in castor wax. do not do.

  Although the invention has been described in terms of specific details, the following examples are merely for the purpose of illustrating the invention and the scope of the invention is defined by the claims. It should be understood that there is.

Example Preparation Example 1 Preparation and Evaluation of Nonionic Emulsion Prepared Using Homogenizer Containing Soy Wax For the purpose of illustrating the present invention, a nonionic emulsion was prepared using Marcus Nut 155 wax (soybean wax). The preparation of the emulsion was carried out using two inert vessels, one for melting the wax and mixing the emulsifier, the other for heating the water to temperature. is there. Once melted and the water rose to temperature, the wax-emulsifier mixture was added to the water heated to the appropriate temperature. The mixture was homogenized using an APV / Goulin homogenizer, a device commonly used in both the chemical and dairy industries. After homogenization, the product may be cooled by a heat exchanger or other container. Homogenizers allow for more intense mixing and can result in a higher solids emulsion than can be obtained using standard mixing techniques.

Method 1) Charge water and set with stirring so that it works well without vortexing.
2) Heat the feed water to 70-80 ° C.
3) Charge Marcus Nut 155 wax.
4) Add nonionic surfactant.
5) Add potassium hydroxide (45% KOH).
6) Hold the mixture at 70-80 ° C. for 30 minutes.
7) Cool to 50 ° C. with stirring.
8) Drain through a homogenizer set at 3000 psi (secondary 500 / primary 2500).
(It should be noted that the temperature and viscosity of the emulsion increase during discharge from the homogenizer)
9) Cool the material to 30-35 ° C. by using a heat exchanger or a second vessel (cooling to 30-35 ° C. reduces the viscosity of the emulsion).

  In this example, the non-ionic surfactant used was IJepal® CO-630 (Rhodia Inc., Cranberry, NJ). The surfactant is selected such that the surfactant has an HLB in the range of 11-12, as indicated as “Target HLB”. The HLB properties of surfactants are well known to those skilled in the art and will not be further described. Therefore, other surfactants having desired characteristics may be used in place of IJEPAR (registered trademark) CO-630. Examples of such alternative surfactants are described above in this specification.

  The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it looked uniform and only a very small amount of non-emulsified wax particles were observed.

Example 2 Preparation and Evaluation of Cationic Emulsion Containing Soy Wax For the purpose of illustrating the present invention, a cationic emulsion was prepared using Marcus Nut 155 wax (soybean base). The preparation of the emulsion was carried out using two inert containers, one for melting the wax and mixing the emulsifier, and the other for heating the water to temperature. When melted and the water rose to temperature, the water heated to temperature and the wax-emulsifier mixture were combined. This technique for emulsification is well known to those skilled in the art as a wax to water technique and utilizes standard mixing techniques to prepare the emulsion.

Method 1) Marcus 155 wax and a cationic surfactant are melted at 60 to 70 ° C.
2) Heat the first feed water to 55-65 ° C.
3) When the first charge water reaches temperature, add glacial acetic acid to the melt in stage 1.
4) Transfer the molten wax, cationic surfactant and acid mixture to heated water.
5) Once all ingredients are transferred, mix for 30 minutes.
6) Cool to 30-35 ° C.
7) Add water to achieve final concentration of 35% solids.

  The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it appeared to be uniform, and a very small amount of non-emulsified wax particles were observed.

Example 3 Preparation and Evaluation of Nonionic Emulsion Containing Soy Wax For the purpose of illustrating the present invention, a nonionic emulsion was prepared using Marcus Nut 155 wax (soybean base). The preparation of the emulsion was carried out using two inert containers, one for melting the wax and mixing the emulsifier, and the other for heating the water to temperature. When melted and the water rose to temperature, the water heated to temperature and the wax-emulsifier mixture were combined. Similar to Example 2, this technique for emulsification is well known to those skilled in the art as a wax-to-water technique.

Method 1) Charge water and set with stirring so that it works well without vortexing.
2) Heat the feed water to 70-80 ° C.
3) Charge Marcus Nut 155 wax.
4) Add nonionic surfactant.
5) Add potassium hydroxide (45% KOH).
6) Hold at 70-80 ° C. for 30 minutes.
7) Cool quickly to 30-35 ° C and maintain good agitation.

  In this example, the nonionic surfactant used was Ijepal (registered trademark) CO-630 (Rhodia). The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it looked uniform and only a trace amount of wax particles was observed.

Example 4 Preparation and Evaluation of Cationic Emulsions Containing Mixtures of Soy Wax and Castor Wax For certain end uses such as floor brighteners, fibers, coatings and inks, wax emulsions are more than waxes used in applications such as cosmetics It needs to be produced using a wax having a high melting point. For the purpose of illustrating the present invention, a cationic emulsion was prepared using Marcus Nut 180 wax, which is a mixture of 30% castor wax and 70% soy wax. The castor wax and soybean wax were prepared by curing castor oil and soybean oil to have a low iodine number, similar to the preparation of soybean wax already described herein. Castor wax and soy wax mixed wax is characterized by the following properties:

  The above materials are also available from Abitec Performance Products under the STEROTEX (R) K trademark and are generally used to coat tablets in the pharmaceutical industry.

  The preparation of the emulsion was carried out using two inert containers, one for melting the wax and mixing the emulsifier, and the other for heating the water to temperature. Once melted and the water rose to temperature, the water heated to temperature and the wax / emulsifier / alkali were combined. This technique for emulsification is well known to those skilled in the art as a wax-to-water technique.

Method 1) Marcus 180 wax and a cationic surfactant are melted at 85 to 90 ° C.
2) Heat the first feed water to 90-95 ° C.
3) When the first charge water reaches temperature, add glacial acetic acid to the melt in stage 1.
4) Transfer the molten wax, cationic surfactant and acid mixture to heated water.
5) Once all ingredients are transferred, mix for 30 minutes.
6) Cool to 30-35 ° C.
7) Add enough water to adjust the solids content to 35%.

  The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it looked uniform and only a trace amount of wax particles was observed.

Example 5 FIG. Preparation and Evaluation of Nonionic Emulsions Containing a Mixture of Soy Wax and Castor Wax Nonionic Emulsions are very versatile and can be prepared due to their broad compatibility and ready availability The surfactants used for this are relatively harmless. To examine whether a mixture of vegetable oil-derived waxes could be emulsified as a nonionic formulation, the soybean-castor wax formulation described in Example 4 was formulated into the following emulsion:

Method 1) Charge water and set with stirring so that it works well without vortexing.
2) Heat the feed water to 90-95 ° C.
3) Charge Marcus Nut 180 wax.
4) A nonionic surfactant is charged.
5) Add potassium hydroxide (45% KOH).
6) Hold the mixture at 90-95 ° C. for 30 minutes.
7) Cool quickly to 30-35 ° C and maintain good agitation.

  In this example, the nonionic surfactant used was IGEPAL (R) CO-630 (Rhodia). Other nonionic surfactants that may be used include HLB 10.5 Tomador® 25-3 / 25-9 combination (Tomer Chemical Corporation) or HLB 10.5 Terditol® 15-S. -5 / 15-S-9 combination (Dow Chemical, Midland, Michigan).

  The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it looked uniform and only a trace amount of wax particles was observed.

Example 6 Preparation and Evaluation of Nonionic Emulsions Containing a Mixture of Soy Wax and Castor Wax and Prepared Using a Homogenizer According to the use of a homogenizer to prepare an emulsion (as used in Example 1), In particular, it is possible to increase the solids content compared to that obtained using conventional stirring techniques such as those used in Examples 4 and 5 above. In order to investigate whether a stable emulsion could be prepared using a mixture of castor wax and soy wax, the following emulsion was prepared:

Method 1) Charge water and set with stirring so that it works well without vortexing.
2) Heat the feed water to 90-95 ° C.
3) Charge Marcus Nut 180 wax.
4) Add nonionic surfactant.
5) Charge potassium hydroxide (45% KOH).
6) Hold at 85-90 ° C. for 30 minutes.
7) Cool to 50 ° C. with stirring.
8) Drain through a homogenizer set at 3000 psi (secondary 500 / primary 2500).
(It should be noted that the temperature and viscosity of the emulsion increase)
9) Cool the material to 30-35 ° C. by using a heat exchanger or a second vessel (cooling to 30-35 ° C. reduces the viscosity of the emulsion).

  In this example, the nonionic surfactant used was Ijepal (registered trademark) CO-630 (Rhodia). The resulting emulsion was milky and stable. When the emulsion was observed on a glass slide, it looked uniform and only a trace amount of wax particles was observed.

Example 7 Water vapor transmission rate (“MVTR”)
Moisture transmission is an important property of wax-based coatings. MVTR shows how quickly moisture penetrates the wax coating and degrades the properties of the substrate. In boxes containing produce where excess moisture causes fruit or vegetable damage, it is preferable to have a low MVTR. Chicken is often transported in a freezing box, which is generally coated with wax and corrugated cardboard that is frozen immediately after filling with chicken (or other food), often by immersion in an ice / water bath. Box (craft paper coated with wax). If the paper is not protected from water, the strength of the box decreases and these types of boxes become impractical.

  In this experiment, MVTR was examined by the improved ASTM D3833 method. The improvement required the use of a clamp to ensure that the corrugated board was adhered to the aluminum cup.

  Coatings were made using a wet film applicator (Bird type) at 1.5-5 mm intervals depending on the viscosity of the test wax. The coating, a 4 inch wide applicator and a 1/2 inch thick plate glass sheet were placed in a 200-250 ° F. oven for 10-15 minutes. The glass was removed from the oven and a piece of corrugated base paper (unbleached kraft paper, well known to those skilled in the art) was placed on the glass. A predetermined volume of a particular coating was placed on one end of the corrugated board, applied to the corrugated board by an applicator, a hot melt coating was manually coated on the corrugated board, and then allowed to solidify at room temperature. Examination of each sample confirmed that the coating weight was between 5.6 and 6.2 lbl / 1000 square feet.

  The results are summarized in Table 5. From this, it can be seen that the soybean oil wax composition has the same MVTR level as the control formulation, although the coating weight is similar. Although the evaluation of applying wax as an emulsion was not performed, the above results indicate the ability of the wax coating to reduce moisture permeation.

Example 8
Evaluation of Emulsions as Fruit Coatings Containing Vegetable Wax Wax emulsions are often used to coat foods to reduce moisture transpiration during transportation, storage, and delivery to the end consumer, thereby enabling citrus fruits Helps preserve fruity products. In order to investigate the effectiveness of a new emulsion against transpiration of moisture in citrus fruits, an emulsion was prepared according to the following formulation and procedure, and then the emulsion was used for fruit coating, followed by weight loss over time Was monitored.

  15 g of Marcus Oil and Chemical (Houston, TX) Nut 155 wax (soybean wax) is placed in a 400 mL SORVAL® (Norwalk, CT) stainless steel chamber and heated until clear Melted on plate. To this molten wax was added 1 g of Polystep® F-5 ethoxylated nonylphenol (12 moles of ethylene oxide) (Stepan Company Northfield, III.) And 1 g of 30% KOH solution. The mixture was maintained in a molten state and stirred for 30 minutes. Separately, 50 g of tap water was heated to boiling. This boiling water was added to the hot melt wax mixture and quickly placed in a Solvar® Omni mixer homogenizer equipped with a Solvar® model number 17183 rotor knife stirrer. The mixer speed was set to 0.5. After 1 minute 30 seconds, the chamber was placed in cold tap water and cooled with continued stirring. After cooling to room temperature, the resulting emulsion was fluid and opaque. This emulsion was named soybean wax emulsion # 1.

  23 g of soy wax emulsion # 1 was added to 230 g of tap water and mixed until uniform. This diluted emulsion was named Coating # 1. Citrus fruits, specifically lemons, were purchased from a local store. Three lemons were immersed in coating # 1 for a few seconds, then removed and placed in a beaker to dry. After 8 hours, weighed three uncoated lemons named uncoated control lemons and three coated lemons named treated lemons, and weighed the initial weight (WI) for the experiment. I named it.

  The lemon was placed in a cool, dry room (about 65-70 ° F.) and weighed periodically. The average results for 3 untreated control lemons and 3 treated lemons are shown in FIG. After 12 days, untreated control lemons showed signs of damage and were no longer weighed. The treated lemon showed no signs of damage even after 15 days, and the experiment was terminated at this point. The weight of each lemon during this period is recorded and named WX, where X is the weight of the lemon on a particular day. The difference between the experimental weight (WX) and the initial weight (WI) was the weight loss, and this difference was then calculated as a percentage of the initial weight, and the percentage of this weight loss was plotted as a function of time.

  The data shown in FIG. 2 shows that the new emulsion was able to reduce the water loss of the treated lemon from 12.8% to 9.2%, thereby reducing the weight loss by 28%.

Example 9 Repulping Test To examine the feasibility of repulping wax-coated paper samples, 1.5 L of hot (about 120 ° F.) tap water was added to the OSTERIZER® Model 6641 blender. (Sunbeam Corp., Ft. Lauderdale, FL). To this was added 3.98 g sodium carbonate. The blender was set at low speed and allowed to run for 1 minute to dissolve the sodium carbonate. The pH of this aqueous solution was about 10. A 5 g wax-coated cardboard base paper sample (prepared as described in Example 7 above) was then added into water. The blender is allowed to run for 10 minutes and then stopped to simply determine whether sample debris is attached to the side of the lid, if so, remove the debris from the lid and drain to the water in the blender. Added back. The blender was then rotated backwards for an additional 10 minutes to complete the mixing cycle. Upon completion, 500 mL was poured out and diluted with an additional 500 mL of hot (ca. 120 ° F.) water. The dilution was poured into the quote jar. The sample is then a control wax sample (the control wax used is a petroleum-derived paraffin wax, BLEND-KOTE (R) 467 (Siggo Petroleum Corporation, Tulsa, Oklahoma)) and subjective And the number and size of the particles present in the liquid were determined as shown in Table 4.

  The results of this evaluation are shown in Table 4. Marcus oil palm wax showed the best repulping results, with the corrugated baseboard sample treated with little visible particles and the coating almost disappeared in the repulping solution. The MVTR of this formulation (Table 6) is higher than the control but is considered to be low to some extent acceptable for most food packaging applications.

  In the repulping experiment, the soy wax sample produced fewer particles than the control, but produced more particles than the coconut wax. As expected, the SIGGO control produced a large number of visible small particles.

  The repulping test in this example was performed with molten wax, but this result shows that the coating shows the result to be achieved when applied in the form of an emulsion (Example 10 below). As shown).

Example 10 Repulping and wet strength testing of emulsion coated paperboard Cardboard paperboard samples were obtained and coated with soy wax emulsions to determine the repulpability of emulsion coated paperboard.

  Test emulsions were prepared using the following formulation:

  Melt the wax by immersing it in a water bath set at 205 ° F. and add KOH solution, surfactant and 50 g hot water into a Solvar® mixer (mixing speed set to 2). The emulsion was prepared by stirring for 15 minutes and rapidly cooling in a tap water bath with continued stirring. The resulting emulsion was a stable and fluid milky emulsion. Polystep® F-3 is a nonionic surfactant having an HLB in the range of 10-12.

  Paperboard, specifically a cardboard box (200 # “C” flute, cardboard craft with 32 lb / in end compression) was cut into 3 cm × 8 cm pieces and each piece weighed. The weighed pieces were dried in an oven set at 90 ° C. for 30 minutes.

  Six pieces (3 treated were named A, 3 controls were named C) were immersed in the emulsion for 5 minutes. These fragments seemed to be completely infiltrated. The other three paperboard pieces (untreated and named B) were left as untreated samples. Six treated pieces (A and C) were removed from the emulsion and dried. All samples were placed in an oven set at 90 ° C. for 1 hour. The weight was recorded as follows:

  To repeat the repulping conditions, each of the dry samples was mixed with 80 mL of tap water and 3 mL of Polystep® F-3 and KOH were added to bring the pH to about 9. The sample was heated to 60 ° C. and mixed for 5 minutes in a Solvar® mixer set at speed # 3. Each sample was filtered through filter paper (20 micron pore size) and washed with warm tap water (3 washes, each wash was approximately 200 mL). The washed pulp was placed in a 90 ° C. oven for 8 hours and dried.

  After drying, 3 g of pulp was taken from each sample and mixed with 40 mL of xylene (a well-known solvent for Marcus Nut 180 wax). The pulp soaked in xylene was placed in an 80 ° C. oven for 30 minutes, then mixed well and left for 30 minutes. 13 g of supernatant xylene was transferred from each beaker to a weighing beaker and then placed on a hot plate to volatilize the solvent. A control sample (emulsion coated corrugated paperboard sample) was prepared and subjected to xylene extraction without first repulping.

  As shown below, this result indicates that the wax has been removed from the paper as a result of washing with warm alkaline water and a surfactant. Control indicates that the correct amount of wax is present if not removed in the repulping step.

  It was observed that the treated sample was clearly harder than the untreated sample. To investigate whether the emulsion coating affects the wet strength properties of the cardboard, further preparation of treated and untreated samples as described in this example above, except that they were not subjected to repulping conditions did. All samples were immersed in room temperature water for 1 minute, then the samples were placed on a scale, a 3/8 inch diameter rod was placed perpendicular to the paper, and the force required to crush the cardboard was measured.

  As shown below, the results show that the new emulsion helps to improve the crush strength of wet corrugated cardboard.

Example 11 Wax and Newspaper Repulping The paper stock used for this evaluation was US News, which is known in the industry to be made using a high percentage of secondary fibers. Because this paper is made with a high content of recycled paper, wax-coated paper stock is often mixed with uncoated paper stock. As long as the wax is not removed, the wax causes problems with the reworked paper. Such problems include paper stains and the effect on paper gloss and printing performance.

  The following evaluations show that the waxes of the present invention can be easily dispersed under normal repulping conditions, and that the saponification of triglyceride waxes to soap helps repulping. Benefits.

  A 10% solids paper solid stock (10 g paper and 90 g water) was produced using a high speed mixer. This paper stock was used as a control pulp stock. By adding any of the emulsions prepared with one of the vegetable waxes, or by adding a surfactant known to be effective in removing ink from paper, a series of A mixture was prepared. The emulsion or surfactant was added to a concentration of either 0.5% or 1.0% depending on the weight of the water bath (ie, depending on the total weight of the paper stock). Each emulsion was added from a product containing 30% actives, while surfactant was added from a stock containing 45% actives (ethylene oxide and propylene oxide).

  The following mixtures were prepared and evaluated for ink removal:

  In this example, the deinking surfactant was Nalco DI 1221, an ethoxylated propylene oxide alcohol supplied by Ondealco, Naperville, Illinois. This surfactant has been developed specifically for deinking applications. The above mixture was stirred for 10 minutes. As further described in this example, the mixture containing the emulsion prepared using wax needed to adjust the pH of the reaction mixture to 7.5-8.0 using sodium hydroxide solution. The paper slurry was then washed to float the ink from the paper, and the paper samples were examined using a Hunter Whiteness scale well known to those skilled in the art.

  As shown below, the results show that both nut (NAT) waxes performed better than the deinking surfactant (Nalco DI 2221) at lower concentrations (0.5%). It is. However, for samples made with nut 180 wax (70% hardened soy wax and 30% hardened castor wax), the processing temperature is increased to 160-175 ° F to improve the solubility of the base wax. It was necessary to let them.

  A second series of experiments was conducted to see if the nut wax performed better than the control deinking surfactant due to the higher ink removal rate from the paper. In this experiment, the sample containing the wax composition of the present invention has an initial 1 minute compared to a deinking surfactant (Nalco DI 2221) that required 8 minutes of processing to achieve the best results. Ink was removed during processing.

  The emulsion used in the above mixture was prepared using an emulsion made with a pH of 6-7 during the emulsification process.

  An emulsion was prepared with Marcus Nut 155 (soybean) using a pH of about 7.8 during the emulsification process, and a sample of this emulsion was used to remove ink from newspaper printing as described above in this example. I investigated. According to these data, an emulsion prepared using a processing pH between 6.0 and 7.0 was used, and an alkali was added during the deinking slurry process to adjust the pH to 7.5 to 8.0. It was shown that the best results were obtained by adjusting to.

Example 12 Effect of pH and Temperature on the Repulpability of Paper Stock In this example, stock paper with no finish applied was used (finish is generally starch and / or starch applied to writing paper) And clay-based coatings). Paper stock is commonly referred to as # 1 white wrapping tissue in the gift wrapping industry and has a basis weight of 10 lbs per 1000 square feet of paper. The source was Federal Paper Board Company, Inc. (Montvale, NJ).

  Repeat this sample of paper stock with Marcus Nut 180 (containing 30% solids and IJepal (registered) so that the final concentration of additional solids is 0.5%, 1.0%, and 1.5%. (Trademark) Soy wax-castor wax mixture prepared with CO-630 nonionic surfactant). No additional surfactant was added to the repulped mixture and the sample pH was measured to be 7.5 and 8.0. The coated paper stock was air dried at 250 ° F. After drying, the coated paper stock was repulped using a high speed blender and compared to a control sample of untreated stock.

  According to the results of this study, samples treated with low levels (0.5%) of wax had normal viscosity within 20 minutes compared to controls that required 42 minutes (untreated paper stock). Pulp was shown to be obtained. Sodium hydroxide was added to raise the pH to 7.5-8.0 and no further heating was performed. A processing temperature of 170-180 ° F. was achieved, and this heat was generated by high speed mixing of the reaction mixture. Samples prepared with high levels of nut 180 wax (1.5%) showed a processing time of 18 seconds.

  From these results, emulsions containing nut 180 (a mixture of soy wax and castor wax) or nut 155 (soybean) wax are present on paper at low levels (0.5-1.5%) and are natural waxes. It has been shown that when the pH is adjusted to convert to a mild soap, it aids the repulping process. The degree of change indicated as the difference in time required to obtain the pulp is considered significant.

  Obviously, modifications and variations of the present invention are possible in light of the above teachings. Therefore, it should be understood that the invention may be practiced within the scope of the appended claims unless otherwise specified.

It is a flowchart which shows the process for manufacturing hardened oil. Figure 3 shows the effect on weight loss of coating citrus fruits with soy wax based emulsions.

Claims (7)

Hardened vegetable wax characterized by having an iodine number of less than 10 and 48.9-93.3 ° C. (120-200 ° F.) (Mettler drop point) of 10% to 50% of the total weight of the emulsion ;
55% to 75% water based on the total weight of the emulsion;
1% to 25% surfactant based on the total weight of the emulsion; and
0.02% to 2.5% acid or base relative to the total weight of the emulsion;
Including
The wax is selected from the group consisting of castor, soybean, palm, corn, cottonseed, rapeseed, canola, sunflower, palm kernel, coconut, cranberry, flaxseed and peanut;
Containing 20% to 45% solids based on the total weight of the emulsion;
A water-wax emulsion applied to the fibrous cellulose product in an amount effective to render the fibrous cellulose product moisture resistant. Wherein the crushing strength of the treated fibrous cellulosic products is improved, emulsion according to claim 1. Wherein the crushing strength of the wet of the treated fibrous cellulosic products is improved, emulsion according to claim 1. The emulsion of claim 1 , wherein the applied emulsion is removed from the moisture resistant fibrous cellulose product by treating the treated moisture resistant fibrous cellulose product with a warm alkaline aqueous mixture. Adding an emulsion of claim 1 in a warm alkaline aqueous mixture comprising a fibrous cellulosic products containing ink, removing said ink, the method of removing the ink from the fibrous cellulosic products. 6. The method of claim 5 , further comprising adding the emulsion to the warm alkaline aqueous mixture in an amount ranging from 0.1% to 1% of the solution. A method for delaying the transpiration rate of water from a fruit, wherein the emulsion according to claim 1 is applied to the fruit in an amount effective to delay the transpiration of water.

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